Highly flowable 1-butene polymer and process for producing the same

ABSTRACT

A 1-butene polymer satisfying the following (1), (2) and either (3) or (3′): a process for producing the polymer; a resin modifier comprising the polymer; and a hot-melt adhesive containing the polymer. (1) The intrinsic viscosity [η] as measured in tetralin solvent at 135° C. is 0.01 to 0.5 dL/g. (2) The polymer is a crystalline resin having a melting point (Tm-D) of 0 to 100° C., the melting point being defined as the top of the peak observed on the highest-temperature side in a melting endothermic curve obtained with a differential scanning calorimeter (DSC) in a test in which a sample is held in a nitrogen atmosphere at −10° C. for 5 min and then heated at a rate of 10° C./min. (3) The stereoregularity index {(mmmm)/(mmrr+rmmr)} is 30 or lower. (3′) The mesopentad content (mmmm) determined from a nuclear magnetic resonance (NMR) spectrum is 68 to 73%.

This is a continuation application of U.S. application Ser. No.10/505,264, filed Feb. 1, 2005, now U.S. Pat. No. 7,309,747, which is a371 of PCT/JP03/01793 filed on Feb. 19, 2003.

TECHNICAL FIELD

The present invention relates to a 1-butene-based polymer that has ahigh-fluidity and is well-balanced between fluidity, tensile modulus andtensile elongation, and fabricability (secondary processability), aprocess for producing the 1-butene-based polymer, a resin modifier madeof the 1-butene-based polymer, and a hot-melt adhesive containing the1-butene-based polymer.

The 1-butene-based polymer of the present invention is suitably used invarious applications such as hot-melt adhesives, sealing agents,modifiers for resins and elastomers, wax blending agents and fillerblending agents.

BACKGROUND ART

Hitherto, as polymers that have relatively low molecular weight andcrystallinity and are usable as hot-melt adhesives, etc., there areknown propylene homopolymers or olefin-based polymers produced bycopolymerizing propylene with ethylene or 1-butene.

However, these polymers are deteriorated in uniformity due to broadmolecular weight distribution and broad composition distributionthereof.

Meanwhile, conventionally, 1-butene polymers have been produced usingmagnesium-supported titanium catalysts (Japanese Patent ApplicationLaid-Open No. Hei 7-145205). However, the thus produced 1-butenepolymers have a non-uniform composition which, therefore, gives adverseinfluences on properties thereof such as occurrence of stickiness andpoor transparency.

In this regard, in recent years, 1-butene polymers having a uniformcomposition have been produced using metallocene catalysts (JapanesePatent Application Laid-Open Nos. Sho 62-119214, Sho 62-121708, Sho62-121707, Sho 62-119213 and Hei 8-225605).

In addition, Japanese Patent Application Laid-Open No. Sho 63-57615discloses high-fluidity 1-butene-based polymers.

However, in any of these conventional methods, since non-crosslinkedmetallocene catalysts are used therein, the obtained polymers are liquidamorphous 1-butene-based polymers. Therefore, these 1-butene-basedpolymers have problems concerning poor surface properties, etc.

Also, hot-melt adhesives used in hot-melt bonding methods in whichhigh-molecular compounds are heat-melted and bonded together, have beenextensively employed in various applications because they are excellentin high-speed coatability, rapid curability, solvent-free applicability,barrier property, energy-saving property, inexpensiveness, etc.

The conventional hot-melt adhesives are mainly composed of resinsprepared by blending a tackifier resin or a plasticizer in a basepolymer such as natural rubbers, ethylene-vinyl acetate copolymers,styrene-butadiene-styrene block copolymers and styrene-isoprene-styreneblock copolymers.

However, since the above base polymers contain a large amount of doublebonds, the hot-melt adhesives produced using such base polymers exhibita poor thermal stability upon heating and, therefore, suffer fromoxidation, gelation, decomposition and discoloration upon coating. Inaddition, there occurs such a problem that portions bonded by thehot-melt adhesives are deteriorated in strength with time.

Further, the hot-melt adhesives are also deteriorated in adhesion tolow-polar substances such as polyethylene and polypropylene.

To solve the deteriorated adhesion to the low-polar substances, therehave been conventionally known hot-melt adhesive resins containingpropylene as a base polymer. Although these resins show an excellentthermal stability, the base polymer contained therein has a too highhardness and is deteriorated in fluidity. As a result, the hot-meltadhesive resins must be applied under a high temperature condition, sothat there occurs such a problem that the thermal stability of theresins becomes lowered under such a high-temperature condition and,therefore, a sufficient adhesion strength cannot be attained.

In this regard, as described above, it is known that propylenehomopolymers as well as olefin-based polymers having relatively lowmolecular weight and crystallinity which are produced by copolymerizingpropylene with ethylene or 1-butene, are usable as the base polymer forthe hot-melt adhesives (Japanese Patent Application Laid-Open No. Hei7-145205).

These polymers are excellent in balance between fluidity, flexibilityand fabricability, but deteriorated in tenacity. Therefore, when thesepolymers are used as an adhesive between an elastomer and a nonwovenfabric, there arises such a problem that the resultant product isdeteriorated in adhesion strength.

For example, there is known the method using low-crystalline polymerswhich are enhanced in tenacity by reducing a stereoregularity thereof(Japanese Patent Application Laid-Open No. 2002-322213). However, whenthe stereoregularity of the polymers is excessively reduced,crystallized portions serving as physical crosslinking points areinsufficient, which rather results in deteriorated tenacity of thepolymers.

On the other hand, when the molecular weight of the polymers increasesto allow the polymers to be entangled with each other and thereby attaina good tenacity, the resultant polymers exhibit a high tenacity, buttend to be deteriorated in fluidity.

Thus, in the conventional hot-melt adhesives, it has been required tocontrol the balance between fluidity and tenacity of the base polymerused therein.

The present invention has been completed to solve the above conventionalproblems. An object of the present invention is to provide a1-butene-based polymer having a uniform composition, a well-controlledstereoregularity, a high fluidity and a high flexibility, a process forproducing the 1-butene-based polymer, and a resin modifier made of the1-butene-based polymer.

A further object of the present invention is to solve the problems as topoor tenacity of the base polymer used in the conventional hot-meltadhesives, and provide a hot-melt adhesive containing the 1-butene-basedpolymer which is excellent in not only balance between fluidity andtenacity, thermal stability under a high temperature condition, andadhesion to low-polar substances, but also heat resistance at the bondedsurface.

DISCLOSURE OF THE INVENTION

As a result of extensive researches for accomplishing the above objects,the inventors have found that the 1-butene-based polymers can beproduced at a high activity in the presence of a polymerization catalystcomposed of (A) a specific transition metal compound and (B) at leastone component selected from the group consisting of (B-1) a compoundcapable of forming an ionic complex by reacting with said transitionmetal compound (A), and (B-2) aluminoxane, and the obtained1-butene-based polymers exhibit a suitable molecular weight distributionand composition distribution as well as a good balance between fluidity,physical property (elastic modulus) and fabricability (melting point).

In addition, the inventors have found that the 1-butene-based polymershaving a zero-shear viscosity η⁰ of 300 Pa·s or lower as an index of thefluidity and a tensile elongation at break of 100% or more as an indexof the tenacity are excellent in balance between fluidity and tenacityas well as fabricability (melting point), and are suitably used as abase polymer for hot-melt adhesives.

The present invention has been accomplished based on the above findings.

Thus, the present invention provides the following 1-butene-basedpolymer, process for producing the 1-butene-based polymer, resinmodifier made of the 1-butene-based polymer, and hot-melt adhesivecontaining the 1-butene-based polymer.

1. A high-fluidity 1-butene-based polymer satisfying the followingrequirements (1), (2) and (3):

(1) an intrinsic viscosity [η] of 0.01 to 0.5 dL/g as measured in atetralin solvent at 135° C.;

(2) a crystalline resin having a melting point (Tm-D) of 0 to 100° C.,the melting point being defined as a top of a peak observed on ahighest-temperature side in a melting endothermic curve obtained by adifferential scanning calorimeter (DSC) when a sample is held in anitrogen atmosphere at −10° C. for 5 min and then heated at atemperature rise rate of 10° C./min; and

(3) a stereoregularity index {(mmmm)/(mmrr+rmmr)} of 30 or lower.

2. A high-fluidity 1-butene-based polymer satisying the followingrequirements (1), (2) and (3′):

(1) an intrinsic viscosity [η] of 0.25 to 0.5 dL/g as measured in atetralin solvent at 135° C.;

(2) a crystalline resin having a melting point (Tm-D) of 0 to 100° C.,the melting point being defined as a top of a peak observed on ahighest-temperature side in a melting endothermic curve obtained by adifferential scanning calorimeter (DSC) when a sample is held in anitrogen atmosphere at −10° C. for 5 min and then heated at atemperature rise rate of 10° C./min; and

(3′) a mesopentad fraction (mmmm) of 68 to 73% as determined from anuclear magnetic resonance (NMR) spectrum.

3. The high-fluidity 1-butene-based polymer according to the aboveaspect 2, wherein said polymer has a zero-shear viscosity η⁰ of 300 Pa·sor lower and a tensile elongation at break of 100% or more.

4. The high-fluidity 1-butene-based polymer according to the aboveaspect 1 or 2, wherein said polymer further satisfies the followingrequirements (4) and (5):

(4) a molecular weight distribution (Mw/Mn) of 4 or lower as measured bygel permeation chromatography (GPC); and

(5) a weight-average molecular weigh (Mw) of 10,000 to 100,000 asmeasured by GPC.

5. A process for producing a high-fluidity 1-butene-based polymer,comprising:

homopolymerizing 1-butene, or copolymerizing 1-butene with ethyleneand/or a C₃ to C₂₀ α-olefin except for 1-butene, in the presence of apolymerization catalyst comprising:

(A) a transition metal compound represented by the following generalformula (I):

wherein M is a metal element belonging to Groups 3 to 10 or lanthanoidof the Period Table;

E¹ and E² are independently a ligand selected from the group consistingof substituted cyclopentadienyl, indenyl, substituted indenyl,heterocyclopentadienyl, substituted heterocyclopentadienyl, amide group,phosphide group, hydrocarbon groups and silicon-containing groups, whichform a cross-linked structure via A¹ and A² and may be same or differentfrom each other;

X is a ligand capable of forming a σ-bond with the proviso that when aplurality of X groups are present, these X groups may be same ordifferent from each other, and may be cross-linked with the other Xgroup, E¹, E² or Y;

Y is a Lewis base with the proviso that when a plurality of Y groups arepresent, these Y groups may be same or different from each other, andmay be cross-linked with the other Y group, E¹, E² or X;

A¹ and A² are divalent cross-linking groups capable of bonding the twoligands E¹ and E² to each other which may be same or different from eachother, and are independently a C₁ to C₂₀ hydrocarbon group, a C₁ to C₂₀halogen-containing hydrocarbon group, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR¹—, —PR¹—, —P(O)R¹—, —BR¹— or —AlR¹— wherein R¹ is ahydrogen atom, a halogen atom, a C₁ to C₂₀ hydrocarbon group or a C₁ toC₂₀ halogen-containing hydrocarbon group;

q is an integer of 1 to 5 given by the formula:[(valence of M)−2]; and

r is an integer of 0 to 3, and

(B) at least one component selected from the group consisting of (B-1) acompound capable of forming an ionic complex by reacting with saidtransition metal compound (A), and (B-2) aluminoxane.

6. The process according to the above aspect 5, wherein 1-butene ishomopolymerized in the presence of the polymerization catalystcontaining an organoboron compound as the component (B).

7. The process according to the above aspect 5, wherein 1-butene iscopolymerized with ethylene and/or a C₃ to C₂₀ α-olefin except for1-butene in the presence of the polymerization catalyst containing anorganoboron compound as the component (B).

8. A process for producing the high-fluidity 1-butene-based polymer asdescribed in the above aspect 1 or 2, comprising:

homopolymerizing 1-butene, or copolymerizing 1-butene with ethyleneand/or a C₃ to C₂₀ α-olefin except for 1-butene, in the presence of apolymerization catalyst comprising:

(A) a transition metal compound represented by the above general formula(I) and (B) at least one component selected from the group consisting of(B-1) a compound capable of forming an ionic complex by reacting withsaid transition metal compound (A), and (B-2) aluminoxane.

9. The process according to the above aspect 8, wherein the component(B) is an organoboron compound.

10. A high-fluidity 1-butene-based polymer produced by the process asdescribed in the above aspect 6 or 7.

11. A 1-butene-based resin modifier comprising the high-fluidity1-butene-based polymer as described in the above 1.

12. A hot-melt adhesive containing the high-fluidity 1-butene-basedpolymer as described in the above 2.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

In the following descriptions, [1] the 1-butene-based polymer, [2] theprocess for producing the 1-butene-based polymer, [3] the 1-butene-basedresin modifier and [4] the hot-melt adhesive containing the1-butene-based polymer are explained in detail.

[1] 1-Butene-Based Polymer

The 1-butene-based polymer according to the aspect 1 of the presentinvention satisfies the following requirements (1) to (3).

(1) an intrinsic viscosity [η] of 0.01 to 0.5 dL/g as measured in atetralin solvent at 135° C.;

(2) a crystalline resin having a melting point (Tm-D) of 0 to 100° C.,the melting point being defined as a top of a peak observed on ahighest-temperature side in a melting endothermic curve obtained by adifferential scanning calorimeter (DSC) when a sample is held in anitrogen atmosphere at −10° C. for 5 min and then heated at atemperature rise rate of 10° C./min; and

(3) a stereoregularity index {(mmmm)/(mmrr+rmmr)l of 30 or lower.

The 1-butene-based polymer according to the aspect 2 of the presentinvention satisfies the following requirements (1), (2) and (3′).

(1) an intrinsic viscosity [η] of 0.25 to 0.5 dL/g as measured in atetralin solvent at 135° C.;

(2) a crystalline resin having a melting point (Tm-D) of 0 to 100° C.,the melting point being defined as a top of a peak observed on ahighest-temperature side in a melting endothermic curve obtained by adifferential scanning calorimeter (DSC) when a sample is held in anitrogen atmosphere at −10° C. for 5 min and then heated at atemperature rise rate of 10° C./min; and

(3′) a mesopentad fraction (mmmm) of 68 to 73% as determined from anuclear magnetic resonance (NMR) spectrum.

The 1-butene-based polymer according to the aspect 1 of the presentinvention has an intrinsic viscosity [η] of 0.01 to 0.5 dL/g as measuredin a tetralin solvent at 135° C. The intrinsic viscosity [η] ispreferably 0.1 to 0.5 dL/g.

If the intrinsic viscosity [η] is less than 0.01 dL/g, the resultantpolymer tends to be deteriorated in physical property (strength). If theintrinsic viscosity [η] exceeds 0.5 dL/g, the resultant polymer tends tobe deteriorated in fluidity.

The 1-butene-based polymer according to the aspect 2 of the presentinvention has an intrinsic viscosity [η] of 0.25 to 0.5 dL/g as measuredin a tetralin solvent at 135° C. The intrinsic viscosity [η] ispreferably 0.30 to 0.5 dL/g.

If the intrinsic viscosity [η] is less than 0.25 dL/g, the resultantpolymer tends to be insufficient in number of molecules bonding betweencrystals, and tends to be deteriorated in tenacity (tensile elongationat break) when used in hot-melt adhesives. If the intrinsic viscosity[η] exceeds 0.5 dL/g, the resultant polymer tends to have a too highviscosity and be deteriorated in fluidity, resulting in occurrence ofdefects upon molding.

The 1-butene-based polymer according to the aspect 1 or 2 of the presentinvention must be a crystalline resin having a melting point (Tm-D) of 0to 100° C. and preferably 0 to 80° C. as measured by differentialscanning calorimeter (DSC) in view of a good softness thereof.

The melting point (Tm-D) is determined by the DSC measurement asfollows.

That is, using a differential scanning calorimeter (“DSC-7” availablefrom Perkin Elmer Corp.), 10 mg of a sample is held in a nitrogenatmosphere at −10° C. for 5 min, and then heated at a temperature riserate of 10° C./minute to prepare a melting endothermic curve. The top ofa peak observed on the highest temperature side in the meltingendothermic curve is defined as the melting point (Tm-D).

The crystalline resin used in the present invention means a resin havingthe measurable melting point (Tm-D).

The 1-butene-based polymer according to the aspect 1 of the presentinvention has a stereoregularity index {(mmmm)/(mmrr+rmmr)} of 30 orlower, preferably 20 or lower and more preferably 15 or lower.

If the stereoregularity index exceeds 30, the resultant polymer tends tobe deteriorated in flexibility and fabricability.

Here, the mesopentad fraction (mmmm) is preferably 20 to 90%, morepreferably 40 to 85% and most preferably 60 to 80%.

If the mesopentad fraction is less than 20%, the resultant moldedarticle tends to exhibit stickiness on its surface or be deteriorated intransparency.

On the other hand, if the mesopentad fraction exceeds 90%, the resultantpolymer tends to be deteriorated in flexibility and fabricability.

The 1-butene-based polymer according to the aspect 2 of the presentinvention has a mesopentad fraction (mmmm) of 68 to 73% and preferably69 to 73%.

If the mesopentad fraction is less than 68%, the resultant polymer tendsto be insufficient in content of crystals serving as physicalcrosslinking points owing to a too low crystallinity thereof. As aresult, the polymer tends to be deteriorated in tensile elongation atbreak when used in hot-melt adhesives.

On the other hand, if the mesopentad fraction exceeds 73%, the resultantpolymer tends to have excessive physical crosslinking points, resultingin deterioration in flexibility and tensile elongation at break.

The 1-butene-based polymer according to the aspect 1 or 2 of the presentinvention contains 1,4-insertion portions in an amount of 5% or lower.

If the content of the 1,4-insertion portions exceeds 5%, the resultantpolymer has a broad composition distribution, resulting in adverseinfluences on physical properties thereof.

In the present invention, the mesopentad fraction (mmmm) and theabnormal insertion content (1,4-insertion fraction) is determinedaccording to the method reported and proposed in Asakura et al.,“Polymer Journal”, 16, 717(1984), J. Randall et al., “Macromol. Chem.Phys.”, C29, 201(1989), and V. Busico et al., “Macromol. Chem. Phys.”,198, 1257(1997).

More specifically, the mesopentad fraction and the abnormal insertioncontent in the molecule of poly(1-butene) are determined by measuringsignals attributed to methylene and methine groups using ¹³C nuclearmagnetic resonance spectrum.

The ¹³C nuclear magnetic resonance spectrum measurement is carried outusing the following apparatus under the following conditions.

Apparatus: ¹³C-NMR spectrometer “JNM-EX400 Model” available from NipponDenshi Co., Ltd.;

Method: proton complete decoupling method;

Sample concentration: 230 mg/mL;

Solvent: mixed solvent of 1,2,4-trichlorobenzene and heavy benzene(volume ratio: 90:10);

Measuring temperature: 130° C.;

Pulse width: 45°;

Pulse repetition period: 4 s; and

Cumulative frequency: 10,000 times

In the present invention, the stereoregularity index{(mmmm)/(mmrr+rmmr)} is calculated from values (mmmm), (mmmr) and (rmmr)measured by the above method.

The 1-butene-based polymer according to the aspect 1 or 2 of the presentinvention has, in addition to the above requirements, a molecular weightdistribution (Mw/Mn) of preferably 4 or lower, more preferably 3.5 orlower and still more preferably 3.0 or lower as measured by GPC.

If the molecular weight distribution (Mw/Mn) exceeds 4, the resultantpolymer tends to suffer from occurrence of stickiness.

Also, the 1-butene-based polymer according to the aspect 1 or 2 of thepresent invention has, in addition to the above requirements, aweight-average molecular weight (Mw) of preferably 10,000 to 100,000 asmeasured by GPC.

If the weight-average molecular weight (Mw) is less than 10,000, theresultant polymer tends to be deteriorated in physical properties(strength).

In addition, if the weight-average molecular weight (Mw) exceeds100,000, the resultant polymer tends to be deteriorated in fluidity,resulting in poor processability.

Meanwhile, the molecular weight distribution (Mw/Mn) is calculated fromthe weight-average molecular weight Mw and number-average molecularweight Mn in terms of polystyrene which are measured by GPC using thefollowing apparatus and conditions:

GPC Measuring Apparatus

-   -   Column: TOSO GMHHR-H(S)HT    -   Detector: RI Detector “WATERS 150C” for liquid chromatogram

Measuring Conditions:

-   -   Solvent: 1,2,4-trichlorobenzene;    -   Measuring temperature: 145° C.;    -   Flow rate: 1.0 mL/min;    -   Sample concentration: 2.2 mg/mL;    -   Amount charged: 160 μL;    -   Calibration curve: Universal Calibration; and    -   Analytic program: HT-GPC (Ver. 10)

The 1-butene-based polymer according to the aspect 1 of the presentinvention has a tensile modulus of preferably 500 MPa or lower and morepreferably 300 MPa or lower as measured in a tensile test according toJIS K-7113.

If the tensile modulus exceeds 500 MPa, the resultant polymer may failto show a sufficient softness.

The 1-butene-based polymer according to the aspect 2 of the presentinvention has a tensile elongation at break of 100% or higher asmeasured in a tensile test according to JIS K-7113 and a zero-shearviscosity η⁰ of less than 300 Pa·s.

If the tensile elongation at break is less than 100%, the resultant1-butene-based polymer tends to be deteriorated in tenacity, so that ahot-melt adhesive using the polymer may fail to attain a sufficientadhesion strength. If the zero-shear viscosity η⁰ is 300 Pa·s or higher,the resultant 1-butene-based polymer tends to be deteriorated incoatability to an adherend due to poor fluidity, resulting in defectsupon molding.

Meanwhile, the zero-shear viscosity η⁰ is measured using the followingapparatus and conditions.

That is, first, using a parallel disk-type rotary rheometer “RMS800”(plate: 50 mmφ; plate intervals: 0.9 mm) available from RheometricsCorp., a 20% sinusoidal shear strain is applied to a sample polymer at120° C. in a range of an angular frequency i of 0.1 to 100 r/s to obtainan absolute value of complex viscosity |η*| thereof. The thus obtainedabsolute value of complex viscosity |η*| is extrapolated to ω=0 r/s tocalculate the zero-shear viscosity η⁰.

The tensile elongation at break and the zero-shear viscosity η⁰ of the1-butene-based polymer are important control factors for the hot-meltadhesives.

The former factor is controlled depending upon the number of moleculesbonding crystals with each other and the number of crystal portions asphysical crosslinking points, and can be mainly controlled by theintrinsic viscosity [η] or molecular weight as well as thestereoregularity of the 1-butene-based polymer, whereas the latterfactor can be controlled by the intrinsic viscosity [η] or molecularweight of the 1-butene-based polymer.

When the 1-butene-based polymer of the present invention is in the formof a copolymer, the copolymer is preferably a random copolymer.

In addition, the content of structural units derived from 1-butene inthe copolymer is preferably 50 mol % or higher and more preferably 70mol % or higher.

If the content of structural units derived from 1-butene in thecopolymer is less than 50 mol %, the resultant copolymer tends to bedeteriorated in fabricability.

Also, when the 1-butene-based polymer of the present invention is in theform of a copolymer, the copolymer has a randomness index of 1 or lessas determined from α-olefin chains according to the follow formula:R=4[αα][BB]/[αB] ²wherein [αα] represents an α-olefin chain fraction; [BB] represents abutene chain fraction; and [αB] represents an c-olefin-butene chainfraction.

The randomness index R is an index representing a degree of randomcopolymerization of the copolymer. The smaller the randomness index R,the higher the isolation of the α-olefin (comonomer) becomes and themore uniform the composition thereof becomes.

The randomness index R is preferably 0.5 or lower and more preferably0.2 or lower.

When the randomness index R is 0, no αα chains are present, and theα-olefin chain is completely composed of an isolated chain solely.

When the 1-butene-based polymer is in the form of a propylene/butenecopolymer, the butene content and randomness index R thereof aredetermined as follows

Specifically, the butene content and randomness index R are calculatedfrom ¹³C-NMR spectrum measured using an NMR apparatus “JNM-EX400 Model”available from Nippon Denshi Co., Ltd., under the following conditions.

Sample concentration: 220 mg/3 mL of NMR solution;

NMR solution: 1,2,4-trichlorobenzene/benzene-d6 (90/10 vol %);

Measuring temperature: 130° C.;

Pulse width: 45°;

Pulse repetition period: 10 s; and

Cumulative frequency: 4,000 times.

Under the above conditions, signals attributed to Sαα carbon in ¹³C-NMRspectrum for PP, PB and BB chains are measured by the method proposed inJ. C. Randall, “Macromolecules”, 1978, 11, 592, to determine PP, PB andBB diad chain fractions in the molecular chain of the copolymer.

From the thus obtained respective diad chain fractions, the butenecontent and the randomness index R are calculated according to thefollowing formulae:Butene Content (mol %)=[BB]+[PB]/2Randomness Index R=4[PP][BB]/[PB] ²wherein [PP] represents a propylene chain fraction; [BB] represents abutene chain fraction; and [PB] represents a propylene-butene chainfraction.

When the 1-butene-based polymer is in the form of an octene/butenecopolymer, the butene content and R thereof are determined as follows.

Specifically, the butene content and randomness index R are calculatedfrom ¹³C-NMR spectrum measured using an NMR apparatus “JNM-EX400 Model”available from Nippon Denshi Co., Ltd., under the following conditions.

Sample concentration: 220 mg/3 mL of NMR solution;

NMR solution: 1,2,4-trichlorobenzene/benzene-d6 (90/10 vol %);

Measuring temperature: 130° C.;

Pulse width: 45°;

Pulse repetition period: 10 s; and

Cumulative frequency: 4,000 times.

Under the above conditions, signals attributed to Sαα carbon in ¹³C-NMRspectrum are measured to obtain OO, OB and BB diad chain fractions inthe molecular chain of the copolymer from the peak intensity valuesderived from BB chain observed at 40.8 to 40.0 ppm, OB chain observed at41.3 to 40.8 ppm and OO chain observed at 42.5 to 41.3 ppm.

From the thus obtained respective diad chain fractions (mol %), thebutene content and randomness index R are calculated according to thefollowing formulae:Butene Content (mol %)=[BB]+[OB]/2Randomness Index R=4[OO][BB]/[OB] ²wherein [OO] represents an octene chain fraction; [BB] represents abutene chain fraction; and [OB] represents an octene-butene chainfraction.[2] Process for Production of 1-Butene-Based Polymer

In the process for production of the 1-butene-based polymer according tothe present invention, the 1-butene-based polymer is produced byhomopolymerizing 1-butene, or copolymerizing 1-butene with ethyleneand/or a C₃ to C₂₀ α-olefin except for 1-butene, in the presence of apolymerization catalyst comprising:

(A) a transition metal compound represented by the following generalformula (I):

wherein M is a metal element belonging to Groups 3 to 10 or lanthanoidof the Period Table;

E¹ and E² are independently a ligand selected from the group consistingof substituted cyclopentadienyl, indenyl, substituted indenyl,heterocyclopentadienyl, substituted heterocyclopentadienyl, amide group,phosphide group, hydrocarbon groups and silicon-containing groups, whichform a cross-linked structure via A¹ and A² and may be same or differentfrom each other;

X is a ligand capable of forming a σ-bond with the proviso that when aplurality of X groups are present, these X groups may be same ordifferent from each other, and may be cross-linked with the other Xgroup, E¹, E² or Y;

Y is a Lewis base with the proviso that when a plurality of Y groups arepresent, these Y groups may be same or different from each other, andmay be cross-linked with the other Y group, E¹, E² or X;

A¹ and A² are divalent cross-linking groups capable of bonding the twoligands E¹ and E² to each other which may be same or different from eachother, and are independently a C₁ to C₂₀ hydrocarbon group, a C₁ to C₂₀halogen-containing hydrocarbon group, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR¹—, —PR¹—, —P(O)R¹—, —BR¹— or —AlR¹— wherein R¹ is ahydrogen atom, a halogen atom, a C₁ to C₂₀ hydrocarbon group or a C₁ toC₂₀ halogen-containing hydrocarbon group;

q is an integer of 1 to 5 given by the formula:[(valence of M)−2]; and

r is an integer of 0 to 3, and

(B) at least one component selected from the group consisting of (B-1) acompound capable of forming an ionic complex by reacting with saidtransition metal compound (A), and (B-2) aluminoxane.

In the above general formula (I), M represents a metal element belongingto Groups 3 to 10 or lanthanoid of the Period Table. Specific examplesof the metal element M include titanium, zirconium, hafnium, yttrium,vanadium, chromium, manganese, nickel, cobalt, palladium and lanthanoidmetals. Of these metal elements, preferred are titanium, zirconium andhafnium from the standpoint of a good catalytic activity forpolymerization of olefins.

E¹ and E² are independently a ligand selected from the group consistingof substituted cyclopentadienyl, indenyl, substituted indenyl,heterocyclopentadienyl, substituted heterocyclopentadienyl, amide group(—N<), phosphide group (—P<), hydrocarbon groups (>CR—, >C<) andsilicon-containing groups (>SiR—, >Si<) wherein R is hydrogen, a C₁ toC₂₀ hydrocarbon group or a hetero atom-containing group, and form across-linked structure via A¹ and A².

The ligands E¹ and E² may be same or different from each other.

Of these ligands E¹ and E², preferred are substituted cyclopentadienyl,indenyl and substituted indenyl.

X represents a ligand capable of forming a σ-bond. When a plurality of Xgroups are present, these X groups may be same or different from eachother, and may be cross-linked with the other X group, E¹, E² or Y.

Specific examples of the ligand X include a halogen atom, a C₁ to C₂₀hydrocarbon group, C₁ to C₂₀ alkoxy, C₆ to C₂₀ aryloxy, a C₁ to C₂₀amide group, a C₁ to C₂₀ silicon-containing group, a C₁ to C₂₀ phosphidegroup, a C₁ to C₂₀ sulfide group and C₁ to C₂₀ acyl.

Y represents a Lewis base. When a plurality of Y groups are present,these Y groups may be same or different from each other, and may becross-linked with the other Y group, E¹, E² or X.

Specific examples of the Lewis base as Y include amines, ethers,phosphines and thioethers.

A¹ and A² are divalent cross-linking groups capable of bonding the twoligands to each other which may be same or different from each other,and are independently represent a C₁ to C₂₀ hydrocarbon group, a C₁ toC₂₀ halogen-containing hydrocarbon group, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR¹—, —PR¹—, —P(O)R¹—, —BR¹— or —AlR¹— wherein R¹ is ahydrogen atom, a halogen atom, a C₁ to C₂₀ hydrocarbon group or a C₁ toC₂₀ halogen-containing hydrocarbon group.

The cross-linking groups include, for example, groups represented by thefollowing general formula:

wherein D is carbon, silicon or tin; R² and R³ are independently ahydrogen atom or a C₁ to C₂₀ hydrocarbon group, and may be same ordifferent from each other and may be bonded to each other to form aring; and e is an integer of 1 to 4. Specific examples of thecross-linking groups represented by the above formula include methylene,ethylene, ethylidene, propylidene, isopropylidene, cyclohexylidene,1,2-cyclohexylene, vinylidene (CH₂═C═), dimethylsilylene,diphenylsilylene, methylphenylsilylene, dimethylgermylene,dimethylstannylene, tetramethyldisilylene and diphenyldisilylene.

Of these cross-linking groups, preferred are ethylene, isopropylideneand dimethylsilylene. The symbol q is an integer of 1 to 5 given by theformula:[(valence of M)−2], and

r is an integer of 0 to 3.

Of these transition metal compounds represented by the above generalformula (I), preferred are transition metal compounds having as aligand, a double crosslinking type biscyclopentadienyl derivativerepresented by the following general formula (II):

In the above general formula (II), M, A¹, A², q and r have the samedefinitions as described previously.

X¹ is a ligand capable of forming a σ-bond, and when a plurality of X¹groups are present, these X¹ groups may be same or different from eachother and may be cross-linked with the other X¹ group or Y¹.

Specific examples of the X¹ groups are the same as exemplified abovewith respect to X of the general formula (I).

Y¹ is a Lewis base, and when a plurality of Y¹ groups are present, theseY¹ groups may be same or different and may be cross-linked with theother Y¹ group or X¹.

Specific examples of the Y¹ groups are the same as exemplified abovewith respect to Y of the general formula (I).

R⁴ to R⁹ are independently a hydrogen atom, a halogen atom, a C₁ to C₂₀hydrocarbon group, a C₁ to C₂₀ halogen-containing hydrocarbon group, asilicon-containing group or a hetero atom-containing group. However, atleast one of R⁴ to R⁹ should be a group other than a hydrogen atom.

Also, R⁴ to R⁹ may be same or different from each other, and adjacenttwo groups thereof may be bonded to each other to form a ring.

In particular, R⁶ and R⁷ as well as R⁸ and R⁹ are preferably bonded toeach other to form a ring.

R⁴ and R⁵ are preferably groups containing a hetero atom such as oxygen,halogen and silicon, because these groups exhibit a high polymerizationactivity.

The transition metal compound containing double crosslinking typebiscyclopentadienyl derivatives as ligands preferably contains siliconin the crosslinking group between the ligands.

Specific examples of the transition metal compounds represented by thegeneral formula (I) include(1,2′-ethylene)(2,1′-ethylene)-bis(indenyl)zirconium dichloride,(1,2′-methylene) (2,1′-methylene)-bis(indenyl)zirconium dichloride,(1,2′-isopropylidene) (2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4,5-benzoindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4,7-diisopropylindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)-bis(4-phenylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(3-methyl-4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(5,6-benzoindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichlorideo, (1,2′-methylene)(2,1′-ethylene)-bis(indenyl)zirconiumdichloride, (1,2′-methylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride,d(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-i-propylindenyl)zirconiumdichloride, (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-phenylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(4,5-benzoindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(4-isopropylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(4,7-di-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(4-phenylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-methyl-4-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(5,6-benzoindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-phenylindenyl)zirconiumdichloride, (1,2′-dimethylsilylene)(2,1′-methylene)-bis(indenyl)zirconium dichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(indenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-i-propylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-isopropylcyclopentadienyl)(3′-methyl-5′-isopropylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-S5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-phenylcyclopentadienyl)(3′-1methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-S5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-S5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride, (1,1′-dimethylsilylene)(2,2′-dimethylsilylene)bisindenylzirconium dichloride,(1,1′-diphenylsilylene)(2,2′-dimethylsilylene)bisindenyl zirconiumdichloride, (1,1′-diisopropylsilylene)(2,2′-dimethylsilylene)bisindenylzirconium dichloride,(1,1′-dimethylsilylene)(2,2′-dilsopropylsilylene)bisindenyl zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-diphenylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-dimethylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-diphenylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-diisopropylsilylene)(2,1′-dimethylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride, (1,2′-dimethylsilylene)(2,1′-diisopropylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-diisopropylsilylene)(2,1′-diisopropylsilylene)(indenyl)(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-diphenylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-dimethylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-diphenylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-diisopropylsilylene)(2,1′-dimethylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-diisopropylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride and(1,2′-diisopropylsilylene)(2,1′-diisopropylsilylene)(indenyl)(3-trimethylsilylmethylindenyl)zirconiumdichloride, as well as compounds obtained by replacing zirconium of theabove-described compounds with titanium or hafnium, though are notlimited thereto.

In addition, similar compounds containing metal elements belonging tothe other Groups or lanthanoid series may also be used in the presentinvention.

Also, in the above-described compounds, the (1,1′-)(2.2′-) substitutedcompounds may be replaced with (1,2′-)(2.1′-) substituted compounds, andthe (1,2′-)(2.1′-) substituted compounds may be replaced with(1,1′-)(2.2′-) substituted compounds.

Among the component (1), the component (B-1) may be selected from anysuitable compounds as long as they are capable of forming an ioniccomplex by reacting with the above transition metal compound (A).Suitable compounds usable as the component (B-1) include coordinationcomplex compounds or Lewis acids composed of an anion and a cationcontaining a plurality of groups bonded to a metal element.

As the coordination complex compounds composed of an anion and a cationcontaining a plurality of groups bonded to a metal element, there may beused various compounds. Examples of the coordination complex compoundssuitably used in the present invention include those compoundsrepresented by the following general formulae (III) and (IV):([L ¹-H] ^(p+))_(q)([M ² X ³ X ⁴ . . . X ^(n)]^((n−m)−))₁   (III)([L ²]^(p+))_(q)([M ³ X ³ X ⁴ . . . X ^(n)]^((n−m)−))   (IV)wherein L¹ represents a Lewis base; L² represents M⁴, R¹⁰R¹¹M⁵ or R¹² ₃Cas defined later; M² and M³ are respectively a metal selected from thegroup consisting of elements belonging to Groups 5 to 15 of the PeriodicTable; M⁴ is a metal selected from the group consisting of elementsbelonging to Group 1 and Groups 8 to 12 of the Periodic Table; M⁵ is ametal selected from the group consisting of elements belonging to Groups8 to 10 of the Periodic Table; X³ to X^(n) are respectively a hydrogenatom, dialkylamino, alkoxy, aryloxy, C₁to C₂₀ alkyl, C₆ to C₂₀ aryl,alkylaryl, arylalkyl, substituted alkyl, an organometalloid group or ahalogen atom; R¹⁰ and R¹¹ are respectively cyclopentadienyl, substitutedcyclopentadienyl, indenyl or fluorenyl; R¹² is alkyl; m represents avalence of M² or M³ and is an integer of 1to 7; n is an integer of 2 to8; p represents an ionic valence of L¹-H or L² and is an integer of 1to7; q is an integer of 1 or more; 1 is a number of q×p/(n−m).

M² and M³ are respectively a metal selected from the group consisting ofelements belonging to Groups 5 to 15 of the Periodic Table, preferablyelements belonging to Groups 13 to 15 of the Periodic Table and morepreferably a boron atom.

M⁴ is a metal selected from the group consisting of elements belongingto Group 1and Groups 8 to 12 of the Periodic Table. Specific examples ofthe M⁴ include respective atoms such as Ag, Cu, Na and Li. M⁵ is a metalselected from the group consisting of elements belonging to Groups 8 to10 of the Periodic Table. Specific examples of the M⁵ include respectiveatoms such as Fe, Co and Ni.

Specific examples of the X³ to X^(n) include dialkylamino groups such asdimethylamino and diethylamino; alkoxy groups such as methoxy, ethoxyand n-butoxy; aryloxy groups such as phenoxy, 2,6-dimethylphenoxy andnaphthyloxy; C₁to C₂₀ alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, n-octyl and 2-ethylhexyl; C₆ to C₂₀ aryl, alkylarylor arylalkyl groups such as phenyl, p-tolyl, benzyl, pentafluorophenyl,3, 5-di(trifluoromethyl)phenyl, 4-tert-butylphenyl, 2,6-dimethylphenyl,3,5-dimethylphenyl, 2,4-dimethylphenyl and 1,2-dimethylphenyl; halogenatoms such as F, Cl, Br and I; and organometalloid groups such aspentamethyl antimony, trimethylsilyl, trimethylgermyl, diphenyl arsine,dicyclohexyl antimony and diphenyl boron.

Specific examples of the substituted cyclopentadienyl groups as R¹⁰ andR¹¹ include methylcyclopentadienyl, butylcyclopentadienyl andpentamethylcyclopentadienyl.

Specific examples of the anion containing a plurality of groups bondedto a metal element include B(C₆F₅)₄ ⁻, B(C₆HF₄)₄ ⁻, B(C₆H₂F₃)₄ ⁻,B(C₆H₃F₂)₄ ⁻, B(C₆H₄F)₄ ⁻, B(C₆(CF₃)F₄)₄ ⁻, B(C₆H₅)₄ ⁻ and BF₄ ⁻.Specific examples of the metal cation include Cp₂Fe⁺, (MeCp)₂Fe⁺,(tBuCp)₂Fe⁺, (Me₂Cp)₂Fe⁺, (Me₃Cp)₂Fe⁺, (Me₄Cp)₂Fe⁺, (Me₅Cp)₂Fe⁺, Ag⁺,Na⁺ and Li⁺. Examples of the other cations include nitrogen-containingcompounds such as pyridinium, 2,4-dinitro-N,N-diethyl anilinium,diphenyl ammonium, p-nitroanilinium, 2,5-dichloroanilinium,p-nitro-N,N-dimethyl anilinium, quinolinium, N,N-dimethyl anilinium andN,N-diethyl anilinium; carbenium compounds such as triphenyl carbenium,tri(4-methylphenyl)carbenium and tri(4-methoxyphenyl)carbenium; alkylphosphonium ions such as CH₃PH₃+, C₂H₅PH₃ ⁺, C₃H₇PH₃ ⁺, (CH₃)₂PH₂ ⁺,(C₂H₅)₂PH₂ ⁻, (C₃H₇)₂PH₂ ⁺, (CH₃)₃PH³⁰ , (C₂H₅)₃PH⁺, (C₃H₆)₇PH⁺,(CF₃)₃PH⁺, (CH₃)₄P⁺, (C₂H₅)₄P⁺ and (C₃H₇)₄P⁺; and aryl phosphonium ionssuch as C₆H₅PH₃ ⁺, (C₆H₅)₂PH₂ ⁺, (C₆H₅)₃PH⁺, (C₆H₅)₄P⁺,(C₂H₅)₂(C₆H₅)PH⁺, (CH₃)(C₆H₅)PH₂ ⁺, (CH₃)₂(C₆H₅)PH⁺ and(C₂H₅)₂(C₆H₅)₂P⁺.

In the present invention, there may be used coordination complexcompounds composed of an optional combination of the above metal cationsand anions.

Specifically, of the compounds represented by the general formulae (III)and (IV), there may be suitably used the following compounds.

Examples of the compounds represented by the general formula (III)include triethyl ammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, trimethyl ammonium tetraphenylborate, triethylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, triethyl ammonium hexafluoroarsenate,pyridinium tetrakis(pentafluorophenyl)borate, pyrroliniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl aniliniumtetrakis(pentafluorophenyl)borate and methyldiphenyl ammoniumtetrakis(pentafluorophenyl)borate.

Whereas, examples of the compounds represented by the general formula(IV) include ferrocenium tetraphenylborate, dimethyl ferroceniumtetrakis(pentafluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, decamethyl ferroceniumtetrakis(pentafluorophenyl)borate, acetyl ferroceniumtetrakis(pentafluorophenyl)borate, formyl ferroceniumtetrakis(pentafluorophenyl)borate, cyano-ferroceniumtetrakis(pentafluorophenyl)borate, silver tetraphenylborate, silvertetrakis(pentafluorophenyl)borate, trityl tetraphenylborate, trityltetrakis(pentafluorophenyl)borate and silver tetrafluoroborate.

The suitable coordination complex compounds are those composed of anon-coordinated anion and a substituted triaryl carbenium. Examples ofthe non-coordinated anion include anions represented by the followinggenera formula (V):(M¹X²X³ . . . X^(n))^((n−m)−)  (V)wherein M¹is an element selected from the group consisting of elementsbelonging to Groups 5 to 15 of the Periodic Table, preferably Groups 13to 15 of the Periodic Table and more preferably a boron atom; X² toX^(n) are respectively a hydrogen atom, dialkylamino, alkoxy, aryloxy,C₁to C₂₀ alkyl, C₆ to C₂₀ aryl (including halogen-substituted aryl),alkylaryl, arylalkyl, substituted alkyl, an organometalloid group or ahalogen atom; m is a valence of M¹; and n is an integer of 2 to 8.

Further, as the non-coordinated anion, there may be used compoundsgenerally called “carborane”.

Also, examples of the substituted triaryl carbenium include cationsrepresented by the following general formula (VI):[CR¹³R¹⁴R¹⁵]⁺  (VI)

In the above general formula (VI), R¹³, R¹⁴ and R¹⁵ are respectively anaryl group such as phenyl, substituted phenyl, naphthyl and anthracenyl,and may be same or different from each other with the proviso that atleast one of R¹³, R¹⁴ and R¹⁵ is substituted phenyl, naphthyl oranthracenyl.

Examples of the substituted phenyl include groups represented by thefollowing general formula (VII):C₆H_(5-k)R¹⁶ _(k)   (VII)

In the above general formula (VII), R¹⁶ is C₁to C₁₀ hydrocarbyl, alkoxy,aryloxy, thioalkoxy, thioaryloxy, amino, amido, carboxyl or a halogenatom; and k is an integer of 1 to 5.

When k is 2 or more, a plurality of the R¹⁶ groups may be same ordifferent from each other.

Specific examples of the non-coordinated anion represented by thegeneral formula (V) include tetra(fluorophenyl)borate,tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate,tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate,tetrakis(trifluoromethylphenyl)borate, tetra(toluyl)borate,tetra(xylyl)borate, (triphenyl, pentafluorophenyl)borate,[tris(pentafluorophenyl), phenyl]borate andtridecahydride-7,8-dicarbaundecaborate.

Specific examples of the substituted triaryl carbenium represented bythe above general formula (VI) include tri(toluyl)carbenium,tri(methoxyphenyl)carbenium, tri(chlorophenyl)carbenium,tri(fluorophenyl)carbenium, tri(xylyl)carbenium,[di(toluyl),phenyl]carbenium, [di(methoxyphenyl), phenyl]carbenium,[di(chlorophenyl), phenyl]carbenium, [toluyl, di(phenyl)]carbenium,[methoxyphenyl, di(phenyl)]carbenium and [chlorophenyl,di(phenyl)]carbenium.

In addition, as the component (B-1) used in the catalyst of the presentinvention, there may also be used compounds represented by the followinggeneral formula (VIII):BR¹⁷R¹⁸R¹⁹   (VIII)wherein R¹⁷, R¹⁸ and R¹⁹ are respectively C₁ to C₂₀ alkyl or C₆ to C₂₀aryl. Namely, any of the boron compounds containing alkyl or arylsubstituent groups bonded to boron may be used as the component (B-1)without any particular limitations.

The alkyl group may also include halogen-substituted alkyl groups, andthe aryl group may also include halogen-substituted aryl groups andalkyl-substituted aryl groups.

Thus, R¹⁷, R¹⁸ and R¹⁹ in the above general formula (VIII) respectivelyrepresent C₁to C₂₀ alkyl or C₆ to C₂₀ aryl. Specific examples of thealkyl and aryl groups include alkyl groups such as methyl, ethyl,propyl, butyl, amyl, isoamyl, isobutyl, octyl and 2-ethylhexyl; and arylgroups such as phenyl, fluorophenyl, tolyl, xylyl and benzyl.

Meanwhile, R¹⁷, R¹⁸ and R¹⁹ may be same or different from each other.

Specific examples of the compounds represented by the above generalformula (VIII) include triphenyl boron, tri(pentafluorophenyl)boron,tri(2,3,4,5-tetrafluorophenyl)boron,tri(2,4,5,6-tetrafluorophenyl)boron,tri(2,3,5,6-tetrafluorophenyl)boron, tri(2,4,6-trifluorophenyl)boron,tri(3,4,5-trifluorophenyl)boron, tri(2,3,4-trifluorophenyl)boron,tri(3,4,6-trifluorophenyl)boron, tri(2,3-difluorophenyl)boron,tri(2,6-difluorophenyl)boron, tri(3,5-difluorophenyl)boron,tri(2,5-difluorophenyl)boron, tri(2-fluorophenyl)boron,tri(3-fluorophenyl)boron, tri(4-fluorophenyl)boron,tri[3,5-di(trifluoromethyl)phenyl]boron,tri[(4-fluoromethyl)phenyl]boron, diethyl boron, diethylbutyl boron,trimethyl boron, triethyl boron, tri(n-butyl)boron,tri(fluoromethyl)boron, tri(pentafluoroethyl)boron,tri(nonafluorobutyl)boron, tri(2,4,6-trifluorophenyl)boron,tri(3,5-difluorophenyl)boron, di(pentafluorophenyl)fluoroboron, diphenylfluoroboron, di(pentafluorophenyl)chloroboron, dimethyl fluoroboron,diethyl fluoroboron, di(n-butyl)fluoroboron,(pentafluorophenyl)difluoroboron, phenyl fluoroboron,(pentafluorophenyl)dichloroboron, methyl difluoroboron, ethyldifluoroboron and (n-butyl)difluoroboron.

Of these compounds, especially preferred is tri(pentafluorophenyl)boron.

Examples of the aluminoxanes as the component (B-2) include chain-likealuminoxanes represented by the following general formula (IX):

wherein R²⁰ is a hydrocarbon group such as C₁to C₂₀, preferably C₁to C₁₂alkyl, alkenyl, aryl and arylalkyl, or a halogen atom; w represents anaverage polymerization degree, i.e., an integer of usually 2 to 50 andpreferably 2 to 40; the respective R²⁰ groups may be the same ordifferent from each other, and

cyclic aluminoxanes represented by the following general formula (X):

wherein R²⁰ and w are the same as defined above.

The above aluminoxanes may be produced by contacting alkyl aluminum witha condensing agent such as water. The contact method is not particularlylimited, and the reaction may be conducted according to any knowncontact methods.

For example, the reaction may be conducted by (1) the method ofdissolving the organoaluminum compound in an organic solvent, and thencontacting the thus obtained solution with water; (2) the method ofadding the organoaluminum compound at an initial stage of thepolymerization, and then adding water thereto at a later stage of thepolymerization; (3) the method of reacting crystal water contained inmetal salts, etc., or water adsorbed in inorganic or organic substances,with the organoaluminum compound; and (4) the method of reactingtetraalkyl dialuminoxane with trialkyl aluminum, and then reacting theobtained reaction product with water.

The aluminoxanes may be insoluble in toluene.

These aluminoxanes may be used alone or in the form of a mixture of anytwo or more thereof.

When using the component (B-1) as the component (B), the molar ratio ofthe catalyst component (A) to the catalyst component (B-1) is preferably10:1 to 1:100 and more preferably 2:1 to 1:10. If the molar ratio of thecomponent (A) to the component (B-1) is out of the above-specifiedrange, the cost performance of the catalyst per unit weight of theobtained polymer is deteriorated and therefore unpractical.

Also, when using the component (B-2) as the component (B), the molarratio of the component (A) to the component (B-2) is preferably 1:1 to1:1,000,000 and more preferably 1:10 to 1:10,000.

If the molar ratio of the component (A) to the component (B-2) is out ofthe above-specified range, the cost performance of the catalyst per unitweight of the obtained polymer is deteriorated and thereforeunpractical.

The components (B-1) and (B-2) as the component (B) may be used alone orin the combination of any two or more thereof.

Further, the molar ratio of the component (A) to the component (B) usedin the present invention is preferably 10:1 to 1:100 and more preferably1:1 to 1:10. If the molar ratio of the component (A) to the component(B) is out of the above-specified range, the cost performance of thecatalyst per unit weight of the obtained polymer is deteriorated andtherefore unpractical.

In the process for production of the 1-butene-based polymer according tothe aspect 1 of the present invention, when the polymerization catalystis composed of the specific transition metal compound (A) and thecompound (B-1) capable of forming an ionic complex by reacting with saidtransition metal compound (A), in particular, the boron-containingcompound, the 1-butene-based polymer can be produced at an extremelyhigh activity as compared to the case where the aluminoxane is used asthe component (B-2)

Whereas, in the process for production of the 1-butene-based polymeraccording to the aspect 2 of the present invention, the use of thepolymerization catalyst composed of the specific transition metalcompound (A) and the aluminoxane as the component (B-2) is preferred.

The polymerization catalyst used in the production process of thepresent invention may further contain an organoaluminum compound as thecomponent (C) in addition to the components (A) and (B).

As the organoaluminum compound (C), there may be used compoundsrepresented by the general formula (XI):R²¹ _(v)AlJ_(3-v)   (XI)wherein R²¹ is C₁ to C₁₀ alkyl; J is a hydrogen atom, C₁to C₂₀ alkoxy,C₆ to C₂₀ aryl or a halogen atom; and v is an integer of 1 to 3.

Specific examples of the compounds represented by the above generalformula (XI) include trimethyl aluminum, triethyl aluminum, triusopropylaluminum, triusobutyl aluminum, dimethyl aluminum chloride, diethylaluminum chloride, methyl aluminum dichloride, ethyl aluminumdichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride,diethyl aluminum hydride and ethyl aluminum sesquichloride.

These organoaluminum compounds may be used alone or in the form of amixture of any two or more thereof.

In the production process of the present invention, the above describedcomponents (A), (B) and (C) may be preliminarily contacted with eachother.

The preliminary contact may be performed, for example, by contacting thecomponent (B) with the component (A), but is not particularly limitedand may be conducted by any known method.

The preliminary contact is effective to improve the catalytic activity,reduce the amount of the component (B) as a co-catalyst, and reduce thecosts required for the catalyst.

Also, when the components (A) and (B) are contacted with each other, inaddition to the above effects, there can be attained such an effect ofincreasing a molecular weight of the obtained polymer.

The preliminary contact temperature is usually in the range of −20 to200° C., preferably −10 to 150° C. and more preferably 0 to 80° C.

The preliminary contact may also be conducted in the presence of aninert hydrocarbon solvent such as aliphatic hydrocarbons and aromatichydrocarbons.

Of these solvents, especially preferred are aliphatic hydrocarbons.

The molar ratio of the catalyst component (A) to the catalyst component(C) is preferably in the range of from 1:1 to 1:10,000 and morepreferably from 1:5 to 1:2,500.

When further using the component (C), the catalyst can be enhanced inpolymerization activity per unit quantity of transition metal used.However, the use of a too large amount of the organoaluminum compound asthe component (C) is uneconomical and rather tends to cause such adefect that a large amount of the component (C) remains in the obtainedpolymer.

In the present invention, at least one of the catalyst components may besupported on a suitable carrier.

The carrier usable in the present invention is not particularly limited,and may be appropriately selected from inorganic oxides, other inorganicmaterials and organic materials. Of these carriers, preferred are thosemade of inorganic oxides or other inorganic materials.

Specific examples of the inorganic oxides used as the carrier includeSiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, Fe₂O₃, B₂O₃, CaO, ZnO, BaO, ThO₂ ormixtures thereof such as silica-alumina, zeolite, ferrite and glassfibers.

Of these inorganic oxides, especially preferred are SiO₂ and Al₂O₃.

The carriers made of the inorganic oxides may further contain a smallamount of carbonates, nitrates, sulfates or the like.

The other inorganic materials used as the carrier may include magnesiumcompounds such as typically MgCl₂ and Mg(OC₂H₅)₂, or complex saltsthereof which are represented by the general formula:MgR²² _(x)X^(η) _(y)

In the above formula, R²² is C₁ to C₂₀ alkyl, C₁ to C₂₀ alkoxy or C₆ toC₂₀ aryl; X^(q) is a halogen atom or C₁ to C₂₀ alkyl; x is a number of 0to 2; and y is a number of 0 to 2 with the proviso that (x+y) is 2.

The R²² groups and the X^(q) groups may be respectively the same ordifferent from each other.

Examples of the organic materials used as the carrier include polymerssuch as polystyrene, styrene-divinylbenzene copolymer, polyethylene,poly-1-butene, substituted polystyrene and polyarylates, starch, carbonor the like.

Of the above carriers, preferred are MgCl₂, MgCl(OC₂H₅) and Mg(OC₂H₅)₂.

Although the properties of the carrier may vary depending upon kind andproduction method thereof, the carrier has an average particle size ofusually 1 to 300 μm, preferably 10 to 200 μm and more preferably 20 to100 μm.

The too small particle size of the carrier leads to increase in amountof fine powder contained in the polymer, and the too large particle sizethereof leads to increase in amount of coarse particles contained in thepolymer, resulting in reduced bulk density of the polymer or clogging ofa hopper.

The carrier has a specific surface area of usually 1to 1,000 m²/g andpreferably 50 to 500 m²/g, and a pore volume of usually 0.1 to 5 m³/gand preferably 0.3 to 3 m³/g.

When the specific surface area or pore volume is out of theabove-specified range, the catalyst activity tends to be deteriorated.

Meanwhile, the specific surface area and pore volume are determined, forexample, from a volume of nitrogen gas absorbed as measured according toBET method.

Further, the carriers made of the inorganic oxides are preferablycalcined at a temperature of usually 150 to 1,000° C. and preferably 200to 800° C.

When at least one of the catalyst components is supported on thecarrier, at least one of the catalyst components (A) and (B), preferablyboth thereof, may be supported thereon.

Said at least one of the catalyst components (A) and (B) may besupported on the carrier by any suitable method without particularlimitations. For example, there may be used the following methods:

(1) Method of mixing at least one of the components (A) and (B) with thecarrier;

(2) Method of treating the carrier with an organoaluminum compound or ahalogen-containing silicon compound, and then mixing the thus-treatedcarrier with at least one of the components (A) and (B) in an inertsolvent;

(3) Method of reacting the carrier, the component (A) and/or thecomponent (B), and an organoaluminum compound or a halogen-containingsilicon compound with each other;

(4) Method of supporting one of the component (A) and the component (B)on the carrier, and then mixing the carrier with the other remainingcomponent;

(5) Method of mixing a reaction product obtained by contacting thecomponent (A) with the component (B), with the carrier; and

(6) Method of contacting the component (A) with the component (B) underthe co-existence of the carrier to react with each other.

In the above methods (4), (5) and (6), the organoaluminum compound asthe component (C) may be added to the reaction system.

The catalyst of the present invention may be prepared by irradiating anelastic wave on the components (A), (B) and (C) upon the contacttherebetween.

As the elastic wave, there may be usually used a sound wave and morepreferably an ultrasonic wave.

More specifically, the ultrasonic wave having a frequency of 1to 1,000kHz and preferably 10 to 500 kHz is preferably used.

The thus-obtained catalyst may be used in the polymerization in the formof a solid obtained after distilling off the solvent therefrom, or maybe directly used in the polymerization.

Alternatively, in the present invention, the catalyst may be produced bysupporting at least one of the component (A) and the component (B) onthe carrier within the polymerization reaction system.

For example, after adding at least one of the component (A) and thecomponent (B) together with the carrier and, if required, theorganoaluminum compound as the optional component (C), olefin such asethylene is added until reaching ordinary pressure to 2 MPa (gauge), andpre-polymerized at a temperature of −20 to 200° C. for about 1 min toabout 2 h to obtain catalyst particles.

In the present invention, the mass ratio of the component (B-1) to thecarrier is preferably in the range of from 1:5 to 1:10,000 and morepreferably from 1:10 to 1:500, and the mass ratio of the component (B-2)to the carrier is preferably in the range of from 1:0.5 to 1:1,000 andmore preferably from 1:1 to 1:50.

When the component (B) is in the form of a mixture of any two or morekinds of components, the mass ratio of each component (B) to the carrierpreferably lies within the above-specified ranges.

Also, the mass ratio of the component (A) to the carrier is preferablyin the range of from 1:5 to 1:10,000 and more preferably from 1:10 to1:500.

If the mass ratio of the component (B)(i.e., the component (B-1) or thecomponent (B-2)) to the carrier, or the mass ratio of the component (A)to the carrier is out of the above-specified range, the catalyticactivity of the obtained catalyst tends to be deteriorated.

The thus-prepared polymerization catalyst of the present invention hasan average particle size of usually 2 to 200 μm, preferably 10 to 150 μmand more preferably 20 to 100 μm; and a specific surface area of usually20 to 1,000 m²/g and preferably 50 to 500 m²/g.

If the average particle size of the polymerization catalyst is less than2 μm, the amount of fine powder contained in the obtained polymer tendsto be increased. If the average particle size of the catalyst exceeds200 μm, the amount of coarse particles contained in the obtained polymertends to be increased.

If the specific surface area of the catalyst is less than 20 m²/g, thecatalytic activity thereof tends to be deteriorated. If the specificsurface area of the catalyst exceeds 1,000 m²/g, the obtained polymertends to be lowered in bulk density.

Also, in the catalyst of the present invention, the amount of thetransition metal per 100 g of the carrier is usually 0.05 to 10 g andpreferably 0.1to 2 g.

If the amount of the transition metal is out of the above-specifiedrange, the catalytic activity of the catalyst tends to be lowered.

The use of the supported catalyst enables production of polymers havingan industrially useful high bulk density and an excellent particle sizedistribution.

The 1-butene-based polymer of the present invention can be produced byhomopolymerizing 1-butene, or copolymerizing 1-butene with ethyleneand/or C₃ to C₂₀ α-olefin (except for 1-butene) in the presence of theabove polymerization catalyst.

Examples of the C₃ to C₂₀ α-olefins include propylene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. In the presentinvention, these α-olefins may be used alone or in the form of a mixtureof any two or more thereof.

The polymerization methods usable in the present invention are notparticularly limited, and include slurry polymerization, vapor-phasepolymerization, bulk polymerization, solution polymerization, suspensionpolymerization or the like. Of these methods, preferred are slurrypolymerization and vapor-phase polymerization.

As to the polymerization conditions, the polymerization temperature isusually from −100 to 250° C., preferably from −50 to 200° C. and morepreferably from 0 to 130° C.

Also, the amounts of the reactants and the catalyst used may becontrolled such that the molar ratio of the raw monomers to the abovecomponent (A) is preferably in the range of 1to 10⁸ and more preferably100 to 10⁵.

Further, the polymerization time is usually from 5 min to 10 h, and thepolymerization reaction pressure is preferably from ordinary pressure to20 MPa (gauge) and more preferably from ordinary pressure to 10 MPa(gauge).

The molecular weight of the obtained polymer may be controlled byappropriately selecting kinds and amounts of respective catalystcomponents used and polymerization temperature, and further byconducting the polymerization in the presence of hydrogen.

Examples of solvents usable in the polymerization include aromatichydrocarbons such as benzene, toluene, xylene and ethyl benzene;alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as pentane, hexane, heptane andoctane; and halogenated hydrocarbons such as chloroform anddichloromethane.

These solvent may be used alone or in the form of a mixture of any twoor more thereof. Also, the monomers such as x-olefins may be used as thesolvent.

Meanwhile, the polymerization may also be performed in the absence of asolvent.

Prior to the substantial polymerization, a preliminary polymerizationmay be conducted using the above polymerization catalyst.

The preliminary polymerization may be conducted by contacting the solidcatalyst component with, for example, a small amount of olefins. Thecontact method is not particularly limited and may be any known method.

Also, the olefins usable in the preliminary polymerization are notparticularly limited, and there may be used the above-described olefins,e.g., ethylene, C₃ to C₂₀ α-olefins or mixtures thereof. The olefinsused in the preliminary polymerization are preferably identical to thoseused in the subsequent substantial polymerization.

The preliminary polymerization temperature is usually from −20 to 200°C., preferably from −10 to 130° C. and more preferably from 0 to 80° C.

The preliminary polymerization may be conducted in the presence of anysuitable solvent such as aliphatic hydrocarbons, aromatic hydrocarbonsand other monomers.

Of these solvents, preferred are aliphatic hydrocarbons.

Also, the preliminary polymerization may be conducted in the absence ofa solvent.

The preliminary polymerization conditions may be suitably controlledsuch that the obtained preliminary polymerization product has anintrinsic viscosity [η] of 0.2 dL/g or higher and preferably 0.5 dL/g orhigher as measured at 135° C. in decalin, and the yield of thepreliminary polymerization product is 1 to 10,000 g and preferably 10 to1,000 g per one millimole of the transition metal contained in thecatalyst.

[3] 1-Butene-Based Resin Modifier

The 1-butene-based resin modifier of the present invention is made ofthe 1-butene-based polymer according to the aspect 1 of the presentinvention.

The 1-butene-based resin modifier of the present invention can exhibit alow melting point, a good softness and a less stickiness, and canprovide a molded article that are excellent in compatibility withpolyolefin resins.

Namely, the 1-butene-based resin modifier of the present invention iscomposed of the specific 1-butene-based polymer and especially includesa slight amount of crystalline portions in poly-l-butene chain moietiesthereof. As a result, the 1-butene-based resin modifier of the presentinvention exhibits a less stickiness and is excellent in compatibilityas compared to conventional modifiers such as soft polyolefin resins.

Further, the 1-butene-based resin modifier of the present invention isexcellent in compatibility with polyolefin-based resins, in particular,polypropylene-based resins.

As a result, the 1-butene-based resin modifier of the present inventionis prevented from undergoing deteriorated surface properties such asstickiness, and exhibits a high transparency as compared to conventionalmodifiers such as ethylene-based rubbers.

In view of the above advantageous properties, the 1-butene-based resinmodifier of the present invention can be suitably used as a modifier forimproving properties such as flexibility and transparency.

Furthermore, the 1-butene-based resin modifier of the present inventionmay also be suitably used as a modifier for improving heat sealabilityand hot tackiness.

[4] Hot-Melt Adhesive

The 1-butene-based polymer according to the aspect 2 of the presentinvention is suitably used as a base polymer for hot-melt adhesives, andis blended with a tackifier resin, a plasticizer, etc., to provide apolyolefin-based hot-melt adhesive that is excellent in thermalstability and fluidity under high temperature conditions, adhesion tolow-polar substances, and heat resistance at a bonding surface.

Examples of the tackifier resin used in the polyolefin-based hot-meltadhesive using the 1-butene-based polymer according to the aspect 2 ofthe present invention as a base polymer, include rosin resins preparedfrom raw turpentine, terpene resins prepared from raw materials such asα-pinene and β-pinene obtained from pine essential oils, petroleumresins obtained by polymerizing unsaturated hydrocarbon-containingfractions by-produced upon thermal cracking of petroleum naphtha, andhydrogenated products thereof.

Examples of the commercially available tackifiers include “I-MARBP-125”, “I-MARB P-100” and “I-MARB P-90” all available from IdemitsuPetrochemical Co., Ltd., “U-MEX” available from Sanyo Kasei Kogyo Co.,Ltd., “HILET T1115” available from Mitsui Chemical Inc., “CLEARONE K100”available from Yasuhara Chemical Co., Ltd., “ECR227” and “ESCOLET 2101”available from Tonex Co., Ltd., “ARCON P100” available from ArakawaChemical Co., Ltd., and “Regalrez 1078” available from Hercules Inc.

Meanwhile, the tackifier resins are preferably the hydrogenated productsin view of compatibility with the 1-butene-based polymer.

Among the hydrogenated products, a hydrogenated petroleum resin that issuperior in thermal stability is desirable.

In the present invention, various additives such as plasticizers,inorganic fillers and antioxidants may be blended in the 1-butene-basedpolymer, if required.

Examples of the plasticizers include paraffin-based process oils,polyolefin-based waxes, phthalic acid esters, adipic acid esters,aliphatic acid esters, glycols, epoxy-based high-molecular plasticizersand naphthene-based oils. Examples of the inorganic fillers includeclay, talc, calcium carbonate and barium carbonate. Examples of theantioxidants include phosphorus-based antioxidants such astris-nonylphenyl phosphite, distearylpentaerythritol diphosphite,“ADEKASTAB 1178” available from Asahi Denka Co., Ltd., “SUMIRISER TNP”available from Sumitomo Chemical Co., Ltd., “IRGAPHOS 168” availablefrom Ciba Specialty Chemicals Corp., and “Sandstab P-EPQ” available fromSand Co., Ltd.; phenol-based anti-oxidants such as2,6-di-t-butyl-4-methyl phenol,n-octadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate, “SUMIRISERBHT” available from Sumitomo Chemical Co., Ltd., and “IRGANOX 1010”available from Ciba Specialty Chemicals Corp.; and sulfur-basedanti-oxidants such as dilauryl-3,3′-thiodipropionate, pentaerythritoltetrais(3-laurylthiopropionate), “SUMIRISER TPL” available from SumitomoChemical Co., Ltd., “YOSHINOX DLTP” available from Yoshitomi SeiyakuCo., Ltd., and “ANTIOX L” available from Nippon Yushi Co., Ltd.

The polyolefin-based hot-melt adhesives using the 1-butene-based polymeraccording to the aspect 2 of the present invention as a base polymerthereof may be used in various applications such as hygienic materials,packaging, book-making, fibers, wood-working, electric materials,tinning, building and bag-making.

The present invention will be described in more detail by reference tothe following examples. However, it should be noted that the followingexamples are only illustrative and not intended to limit the inventionthereto.

First, methods for evaluating resin properties of the 1-butene-basedpolymers obtained by the production process of the present invention areexplained.

(1) Production of Press-Molded Sheet

(i) Preparation of Sample for Press-Molding

Forty grams of a 1-butene-based polymer was intimately mixed with 1,000ppm of “IRGANOX 1010” available from Ciba Specialty Chemicals Corp., and300 mL of toluene at 80° C. to prepare a uniform polymer solution.

The thus prepared 1-butene-based polymer solution was dried in a draftfor 12 h, and then dried by a dryer at 60° C. to completely removetoluene therefrom, thereby obtaining a sample for press-molding.

(ii) Press-Molding Method

Twenty grams of the sample obtained in the above step (i) was pressedunder a pressure of 50 kg/cm² at 150° C. for 10 min while taking care soas not to trap air bubbles therein, and thereafter gradually cooled toroom temperature to obtain a press-molded sheet having a size of 200mm×200 mm×1 mm.

(2) Measurement for Mesopentad Fraction, Abnormal Insertion Content andStereoregularity Index

Measured by the methods described in the present specification.

(3) Measurement for Comonomer Content

Measured by the method described in the present specification.

(4) Measurement for Intrinsic Viscosity [η]

The intrinsic viscosity of the polymer was measured at 135° C. in atetralin solvent using an automatic viscometer “VMR-053 Model” availablefrom Rigosha Co., Ltd.

(5) Measurement for Weight-Average Molecular Weight (Mw) and MolecularWeight Distribution (Mw/Mn)

Measured by the method described in the present specification.

(6) DSC Measurement (Measurement for Melting Point: Tm-D)

Measured by the method described in the present specification.

More specifically, using a differential scanning calorimeter “DSC-7”available from Perkin Elmer Corp., 10 mg of a sample was held in anitrogen atmosphere at −10° C. for 5 min, and then heated at atemperature rise rate of 10° C./min to prepare a melting endothermiccurve thereof. The melting point (Tm-D) was defined as a top of a peakobserved on the highest-temperature side in the thus prepared meltingendothermic curve.

Also, the melting endotherm as determined upon the above measurement wasexpressed by ΔH-D.

(7) Measurement for Tensile Modulus and Tensile Elongation at Break

A dumbbell-shaped specimen was prepared from the press-molded sheetobtained in the above (1), and subjected to a tensile test according toJIS K-7113 under the following condition.

Cross-head speed: 50 mm/min

(8) Measurement for Zero-Shear Viscosity

Measured by the method described in the present specification.

EXAMPLE 1 (1) Production of Catalyst: Production of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride

A solution prepared by dissolving 3.0 g (6.97 mM) of a lithium salt of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indene) in 50 mL ofTHF (tetrahydrofuran) was charged into a Schlenk's bottle, and cooled to−78° C.

Then, 2.1 mL (14.2 mM) of iodomethyl trimethylsilane was slowly droppedto the solution, and the mixture was stirred at room temperature for 12h.

The resultant reaction solution was distilled to remove the solventtherefrom, and then after adding 50 mL of ether thereto, the reactionsolution was washed with a saturated ammonium chloride solution.

An organic phase separated from the solution was dried to remove thesolvent therefrom, thereby obtaining 3.04 g (5.88 mM) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindene) (yield:84%).

Next, a Schlenk's bottle was charged with 3.04 g (5.88 mM) of the thusobtained (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindene) and 50 mL ofether under a nitrogen flow.

After the contents of the bottle were cooled to −78° C., 7.6 mL of ahexane solution 1.54 M/L of n-BuLi (1.7 mM) was dropped thereto.

The temperature of the resultant mixture was raised to room temperature,and then stirred at room temperature for 12 h. Then, the ether wasdistilled away from the reaction mixture.

The thus obtained solid was washed with 40 mL of hexane to obtain 3.06 g(5.07 mM) of a lithium salt in the form of an ether adduct (yield: 73%).

The results of ¹H-NMR (90 MHz, THF-d₈) measurement of the obtainedproduct were as follows:

δ: 0.04 (s, 18H, trimethylsilyl); 0.48 (s, 12H, dimethylsilylene); 1.10(t, 6H, methyl); 2.59 (s, 4H, methylene); 3.38 (q, 4H, methylene);6.2-7.7 (m, 8H, Ar—H)

The thus obtained lithium salt was dissolved in 50 mL of toluene under anitrogen flow.

After the resultant solution was cooled to −78° C., a suspensionprepared by dispersing 1.2 g (5.1 mM) of zirconium tetrachloride in 20mL of toluene which was previously cooled to −78° C., was dropped intothe solution.

After completion of the dropping, the resultant mixture was stirred atroom temperature for 6 h. The resultant reaction solution was distilledto remove the solvent therefrom.

The obtained distillation residue was recrystallized withdichloromethane, thereby obtaining 0.9 g (1.33 mM) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride (yield: 26%).

The results of ¹H-NMR (90 MHz, CDCl₃) measurement of the obtainedproduct were as follows:

δ: 0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene);2.51 (dd, 4H, methylene); 7.1-7.6 (m, 8H, Ar—H)

(2) Polymerization

An one liter autoclave previously heat-dried was charged with 200 mL ofheptane, 200 mL of 1-butene and 0.5 mM of triisobutyl aluminum, and thenhydrogen was introduced into the autoclave until reaching 0.2 MPa.

After heating the contents of the autoclave to 65° C. while stirring,0.8 μM of triphenyl carbenium tetrakispentafluorophenyl borate and 0.2μM of (1,2′-dimethylsilylene)

(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride were added thereto, and the polymerization was conducted for5 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 13 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 1.

EXAMPLE 2

An one liter autoclave previously heat-dried was charged with 200 mL ofheptane, 200 mL of 1-butene and 0.5 mM of triisobutyl aluminum, and thenhydrogen was introduced into the autoclave until reaching 0.3 MPa.

After heating the contents of the autoclave to 65° C. while stirring,propylene was further continuously introduced into the autoclave until atotal pressure thereof reached 0.8 MPa. Then, 0.8 μM of triphenylcarbenium tetrakispentafluorophenyl borate and 0.2 μM of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride were added to the autoclave, and the polymerization wasconducted for 5 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 14 g of a 1-butenecopolymer.

The resin properties and physical properties of the thus obtained1-butene copolymer were evaluated by the above-described methods. Theresults are shown in Table 1.

EXAMPLE 3

An one liter autoclave previously heat-dried was charged with 200 mL ofheptane, 200 mL of 1-butene, 10 mL of 1-octene and 0.5 mM of triusobutylaluminum, and then hydrogen was introduced into the autoclave untilreaching 0.2 MPa.

After heating the contents of the autoclave to 65° C. while stirring, 2μM of triphenyl carbenium tetrakispentafluorophenyl borate and 0.5 μM of(1,2′-dimethylsilylene)

(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride were added to the autoclave, and the polymerization wasconducted for 5 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 13 g of a 1-butenecopolymer.

The resin properties and physical properties of the thus obtained1-butene copolymer were evaluated by the above-described methods. Theresults are shown in Table 1.

EXAMPLE 4

A ten liter autoclave previously heat-dried was charged with 4 L ofheptane and 2.5 kg of 1-butene, and then hydrogen was introduced intothe autoclave until reaching 0.2 MPa.

After heating the contents of the autoclave to 80° C. while stirring, 5mM of triusobutyl aluminum, 5 μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride and 25 μM of dimethyl anilinium tetrakispentafluorophenylborate were added to the autoclave, and the polymerization was conductedfor 60 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 1.2 kg of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 1.

EXAMPLE 5

A ten liter autoclave previously heat-dried was charged with 4 L ofheptane and 2.5 kg of 1-butene, and then hydrogen was introduced intothe autoclave until reaching 0.03 MPa.

After heating the contents of the autoclave to 80° C. while stirring, 5mM of triusobutyl aluminum, 10 μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-trimethylsilylmethylindenyl)(indenyl)zirconiumdichloride and 50 μM of dimethyl anilinium tetrakispentafluorophenylborate were added to the autoclave, and the polymerization was conductedfor 40 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 1.3 kg of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 1.

COMPARATIVE EXAMPLE 1

The same procedure as in EXAMPLE 1was repeated except for replacing 0.8μM of triphenyl carbenium tetrakispentafluorophenyl borate with 0.25 mMof methyl aluminoxane, and using(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylindenyl)zirconiumdichloride in an amount of 0.25 μM. The polymerization reaction wasconducted for 30 min, and the resultant reaction product was dried inthe same manner as in EXAMPLE 1, thereby obtaining 10 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 1.

From the comparison between EXAMPLE 1 and COMPARATIVE EXAMPLE 1 bothrelating to the production of 1-butene polymers, it was confirmed thatCOMPARATIVE EXAMPLE 1 using methyl aluminoxane instead of theorganoboron compound was deteriorated in catalytic activity. The sametendency was recognized in EXAMPLES 2 and 3 relating to the productionof 1-butene copolymers and EXAMPLES 4 and 5 relating to the productionof 1-butene polymers, namely COMPARATIVE EXAMPLE 1 was deteriorated incatalytic activity as compared to these EXAMPLES.

In addition, the polymers obtained in these EXAMPLES showed a lowerweight-average molecular weight and a lower intrinsic viscosity [η] ascompared to those of COMPARATIVE EXAMPLES.

That is, in the EXAMPLES of the present invention, high-fluidity1-butene-based polymers were produced.

As recognized from EXAMPLES 4 and 5, since the catalysts used in theseEXAMPLES had an excellent heat resistance, it was possible to raise thepolymerization temperature while maintaining the high catalyticactivity. Further, since the catalysts exhibited a high sensitivity tohydrogen, it was also possible to produce suitable 1-butene-basedpolymers having a high fluidity.

TABLE 1 Com. Examples Ex. 1 2 3 4 5 1 Mesopentad fraction (mmmm) 71.2 —— 68.0 68.5 72 (mol %) Abnormal insertion content 0 — — 0 0 0(1,4-insertion fraction) (mol %) Kind of comonomer — * ** — — —Comonomer content (mol %) — 27 3 — — — Stereoregularity index 8 9 9 7 78 (mmmm/(mmrr + rmmr) Intrinsic viscosity [η] (dL/g) 0.4 0.4 0.4 0.220.27 1.0 Weight-average molecular weight × 10⁴ 8 9 8 3.3 4.8 28 (Mw)Molecular weight distribution 2.0 2.0 2.0 1.9 2.7 2.0 (Mw/Mn) Meltingpoint (Tm − D) (° C.) 67 41 46 70.6 67 65 Melting endotherm (ΔH) (J/g)38 14 29 37.8 24 40 Tensile modulus (MPa) 270 60 105 160 172 200Elongation at break (%) 120 650 510 5.3 11 470 Note *: propylene; **:1-octene

EXAMPLE 6

A 10 L autoclave previously heat-dried was charged with 4,000 mL ofheptane, 4,000 mL of 1-butene, 4.0 mM of triusobutyl aluminum and 15 mMof methyl aluminoxane, and then hydrogen was introduced into theautoclave until reaching 0.4 MPa.

After heating the contents of the autoclave to 70° C. while stirring, 15μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride was added to the autoclave, and the polymerization wasconducted for 120 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 1,530 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 2.

EXAMPLE 7

An one liter autoclave previously heat-dried was charged with 200 mL ofheptane, 200 mL of 1-butene, 0.5 mM of trilsobutyl aluminum and 0.4 mMof methyl aluminoxane, and then hydrogen was introduced into theautoclave until reaching 0.4 Pa.

After heating the contents of the autoclave to 60° C. while stirring,0.4 μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride was added to the autoclave, and the polymerization wasconducted for 60 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 44 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 2.

COMPARATIVE EXAMPLE 2

A 10 L autoclave previously heat-dried was charged with 4,000 mL ofheptane, 4,000 mL of 1-butene, 4.0 mM of triusobutyl aluminum and 20 μMof dimethyl anilinium borate, and then hydrogen was introduced into theautoclave until reaching 0.2 Pa.

After heating the contents of the autoclave to 60° C. while stirring, 5μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride was added to the autoclave, and the polymerization wasconducted for 60 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 1,180 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 2.

COMPARATIVE EXAMPLE 3

The same procedure as in EXAMPLE 6 was repeated except for changing thepolymerization temperature to 50° C. The polymerization reaction wasconducted for 120 min, thereby obtaining 980 g of a 1-butene-basedpolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 2.

COMPARATIVE EXAMPLE 4

A 10 L autoclave previously heat-dried was charged with 4,000 mL ofheptane, 4,000 mL of 1-butene, 4.0 mM of triisobutyl aluminum and 5 μMof methyl aluminoxane, and then hydrogen was introduced into theautoclave until reaching 0.6 Pa.

After heating the contents of the autoclave to 50° C. while stirring, 5μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride was added to the autoclave, and the polymerization wasconducted for 180 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 450 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 2.

COMPARATIVE EXAMPLE 5

An one liter autoclave previously heat-dried was charged with 200 mL ofheptane, 200 mL of 1-butene, 0.5 mM of triusobutyl aluminum and 0.8 μMof dimethyl anilinium borate, and then hydrogen was introduced into theautoclave until reaching 0.03 Pa.

After heating the contents of the autoclave to 80° C. while stirring,0.2 μM of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride was added to the autoclave, and the polymerization wasconducted for 30 min.

After completion of the polymerization reaction, the resultant reactionproduct was dried under reduced pressure to obtain 25 g of a 1-butenepolymer.

The resin properties and physical properties of the thus obtained1-butene polymer were evaluated by the above-described methods. Theresults are shown in Table 2.

The polymers obtained in the above EXAMPLES 1 to 7 and COMPARATIVEEXAMPLES 2, 4 and 5 exhibited a high fluidity and a high flexibility ascompared to that obtained in COMPARATIVE EXAMPLE 1. In particular, thepolymers obtained in EXAMPLES 1, 6 and 7 exhibited a high tenacity inaddition to higher fluidity and high flexibility.

The polymer obtained in COMPARATIVE EXAMPLE 2 had a low tensileelongation at break owing to its low intrinsic viscosity [η]. On theother hand, the polymer having a too large intrinsic viscosity [η] asproduced in COMPARATIVE EXAMPLE 3 exhibited a good tensile elongation atbreak, but was deteriorated in fluidity due to its large zero-shearviscosity.

The polymer obtained in COMPARATIVE EXAMPLE 4 had a too highstereoregularity, and the polymer obtained in COMPARATIVE EXAMPLE 5 hada too low stereoregularity. Therefore, both of the polymers weredeteriorated in tensile elongation at break.

TABLE 2 Examples Comparative Examples 6 7 2 3 4 5 [η] (dL/g) 0.36 0.410.22 0.57 0.38 0.32 Tm (° C.) 71 82.4 70.6 81.7 73.9 70.3 (mmmm) (%)70.3 72.4 68.5 73.1 75.2 67.5 Mw 65800 79000 37000 127000 69800 58100Mw/Mn 1.78 1.78 1.9 1.81 1.74 2.35 Tensile elongation at break 130 2405.3 370 99 12 (%) Tensile modulus (MPa) 233 245 160 221 255 236Zero-shear viscosity (Pa · s) 47.9 194 10 479 91 41

INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to produce a1-butene-based polymer having a uniform composition, a well-controlledstereoregularity, a high fluidity and a high flexibility.

In addition, the 1-butene-based resin modifier of the present inventioncan provide a molded article exhibiting a good softness, a lessstickiness and an excellent compatibility with polyolefin resins.

Further, the hot-melt adhesive of the present invention is excellent inthermal stability and fluidity under high temperature conditions,adhesion to low-polar substances and heat resistance at a bondedsurface.

1. A 1-butene-based resin modifier comprising a high-fluidity1-butene-based polymer satisfying the following requirements (1), (2),and (3): (1) has an intrinsic viscosity [η] of 0.01 to 0.5 dL/g asmeasured in a tetralin solvent at 135° C.; (2) is a crystalline resinhaving a melting point (Tm-D) of 0 to 100° C., the melting point beingdefined as a top of a peak observed on a highest-temperature side in amelting endothermic curve obtained by a differential scanningcalorimeter (DSC) when a sample is held in a nitrogen atmosphere at −10°C. for 5 min. and then heated at a temperature rise rate of 10° C/min.;and (3) has a stereoregularity index {(mmmm)/(mmrr+rmmr)} of 30 orlower, produced by a process comprising: homopolymerizing 1-butene, orcopolymerizing 1-butene with ethylene and/or a C₃ to C₂₀ α-olefin exceptfor 1-butene, in the presence of a polymerization catalyst comprising:(A) a transition metal compound having as a ligand, a doublecrosslinking type biscyclopentadienyl derivative represented by thefollowing general formula (II):

wherein M is a metal element belonging to Groups 3 to 10 or lanthanoidof the Periodic Table; X¹ is a ligand that forms a σ-bond with theproviso that when a plurality of X¹ groups are present, these X¹ groupsmay be the same or different from each other and may be cross-linkedwith the other X¹ or Y¹; Y¹ is a Lewis base with the proviso that when aplurality of Y¹ groups are present, these Y¹ groups may be the same ordifferent and may be cross-linked with the other Y¹ group or X¹; R⁴ andR⁵ are independently a hydrogen atom, a halogen atom, a C₁ to C₂₀hydrocarbon group, a C₁ to C₂₀ halogen-containing hydrocarbon group, asilicon-containing group or a hetero atom-containing group, and R⁶ andR⁷ as well as R⁸ and R⁹ are bonded to each other to form a ring; A¹ andA² are divalent cross-linking groups which may be the same or differentfrom each other, and are independently a C₁ to C₂₀ halogen-containinghydrocarbon group, a silicon-containing group, a germanium-containinggroup, a tin-containing group, —O—, —CO—, —S—, —SO₂—, —Se—, —NR¹—,—PR¹—, —P(O)R¹—, —BR¹— or —AlR¹— wherein R¹ is a hydrogen atom, ahalogen atom, or a C₁ to C₂₀ halogen-containing hydrocarbon group; q isan integer of 1 to 5 given by the formula: [(valence of M)−2]; and r isan integer of 0 to 3; and (B) at least one component selected from thegroup consisting of (B-1) a compound capable of forming an ionic complexby reacting with said transition metal compound (A), and (B-2)aluminoxane.
 2. The 1-butene-based resin modifier according to claim 1,which has an intrinsic viscosity of 0.1 to 0.5 dL/g.
 3. The1-butene-based resin modifier according to claim 1, wherein the1-butene-based polymer has a melting point of 0 to 80° C.
 4. The1-butene-based resin modifier according to claim 1, wherein the1-butene-based polymer has a stereoregularity index of 20 or lower. 5.The 1-butene-based resin modifier according to claim 1, wherein the1-butene-based polymer has a mesopentad fraction (mmmm) of 20 to 90%. 6.The 1-butene-based resin modifier according to claim 1, wherein the1-butene-based polymer has 1,4-insertion portions in an amount of 5% orlower.
 7. The 1-butene-based resin modifier according to claim 1,wherein the 1-butene-based polymer has a molecular weight distribution(Mw/Mn) of 4 or lower.
 8. The 1-butene-based resin modifier according toclaim 1, wherein the 1-butene-based polymer has a weight-averagemolecular weight of 10,000 to 100,000 as measured by GPC.
 9. The1-butene-based resin modifier according to claim 1, wherein the1-butene-based polymer has a tensile modulus of 500 MPa or lower. 10.The 1-butene-based resin modifier according to claim 1, wherein thepolymer is a random copolymer, and the content of structural unitsderived from 1-butene in the copolymer is 50 mol% or higher.
 11. The1-butene-based resin modifier according to claim 10, wherein thecopolymer has a randomness index of 1 or less as determined fromα-olefin chains according to the follow formula:R=4[αα][BB]/[αB]² wherein [αα] represents an α-olefin chain fraction;[BB] represents a butene chain fraction; and [αB] represents anα-olefin-butene chain fraction.
 12. A hot melt adhesive comprising ahigh-fluidity 1-butene-based polymer satisfying the followingrequirements (1), (2), and (3′): (1) has an intrinsic viscosity [η] of0.25 to 0.5 dL/g as measured in a tetralin solvent at 135° C.; (2) is acrystalline resin having a melting point (Tm-D) of 0 to 100° C., themelting point being defined as a top of a peak observed on ahighest-temperature side in a melting endothermic curve obtained by adifferential scanning calorimeter (DSC) when a sample is held in anitrogen atmosphere at −10° C. for 5 min. and then heated at atemperature rise rate of 10° C./min,; and (3′) has a mesopentad fraction(mmmm) of 68 to 73% as determined from a nuclear magnetic resonance(NMR) spectrum, produced by a process comprising: homopolymerizing1-butene, or copolymerizing 1-butene with ethylene and/or a C₃ to C₂₀α-olefin except for 1-butene, in the presence of a polymerizationcatalyst comprising: (A) a transition metal compound having as a ligand,a double crosslinking type biscyclopentadienyl derivative represented bythe following general formula (II):

wherein M is a metal element belonging to Groups 3 to 10 or lanthanoidof the Periodic Table; X¹ is a ligand that forms a a-bond with theproviso that when a plurality of X¹ groups are present, these X¹ groupsmay be the same or different from each other and may be cross-linkedwith the other X¹ or Y¹; Y¹ is a Lewis base with the proviso that when aplurality of Y¹ groups are present, these Y¹ groups may be the same ordifferent and may be cross-linked with the other Y¹ group or X¹; R⁴ andR⁵ are independently a hydrogen atom, a halogen atom, a C₁ to C₂₀hydrocarbon group, a C₁ to C₂₀ halogen-containing hydrocarbon group, asilicon-containing group or a hetero atom-containing group, and R⁶ andR⁷ as well as R⁸ and R⁹ are bonded to each other to form a ring; A¹ andA² are divalent cross-linking groups which may be the same or differentfrom each other, and are independently a C₁ to C₂₀ halogen-containinghydrocarbon group, a silicon-containing group, a germanium-containinggroup, a tin-containing group, —O—, —CO—, —S—, —SO₂—, —Se—, —NR¹—,—PR¹—, —P(O)R¹—, —BR¹— or —AIR¹— wherein R¹ is a hydrogen atom, ahalogen atom, or a C₁ to C₂₀ halogen-containing hydrocarbon group; q isan integer of 1 to 5 given by the formula: [(valence of M)−2]; and r isan integer of 0 to 3; and (B) at least one component selected from thegroup consisting of (B-1) a compound capable of forming an ionic complexby reacting with said transition metal compound (A), and (B-2)aluminoxane.
 13. The hot melt adhesive according to claim 12, whereinthe 1-butene-based polymer has an intrinsic viscosity of 0.3 to 0.5dL/g.
 14. The hot melt adhesive according to claim 12, wherein the1-butene-based polymer has a melting point of 0 to 80° C.
 15. The hotmelt adhesive according to claim 12, wherein the 1-butene-based polymercontains 1,4-insertion portions in an amount of 5% or lower.
 16. The hotmelt adhesive according to claim 2, wherein the 1-butene-based polymerhas a molecular weight distribution (Mw/Mn) of 4 or lower.
 17. The hotmelt adhesive according to claim 12, wherein the 1-butene-based polymerhas a weight-average molecular weight of 10,000 to 100,000 as measuredby GPC.
 18. The hot melt adhesive according to claim 12, wherein the1-butene-based polymer has a tensile elongation at break of 100% orhigher as measured in a tensile test according to JIS K-7113 and azero-shear viscosity η⁰ of less than 300 Pa·s.
 19. The hot melt adhesiveaccording to claim 12, wherein the polymer is a random copolymer, andthe content of structural units derived from 1-butene in the copolymeris 50 mol% or higher.
 20. The hot melt adhesive according to claim 19,wherein the copolymer has a randomness index of 1 or less as determinedfrom α-olefin chains according to the follow formula:R=4[αα][BB]/[αB]² wherein [αα] represents an α-olefin chain fraction;[BB] represents a butene chain fraction; and [αB] represents ana-olefin-butene chain fraction.